CN220376750U - Recovery device for copper-containing etching waste liquid - Google Patents
Recovery device for copper-containing etching waste liquid Download PDFInfo
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- CN220376750U CN220376750U CN202320465227.8U CN202320465227U CN220376750U CN 220376750 U CN220376750 U CN 220376750U CN 202320465227 U CN202320465227 U CN 202320465227U CN 220376750 U CN220376750 U CN 220376750U
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- waste liquid
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- 239000007788 liquid Substances 0.000 title claims abstract description 117
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000010949 copper Substances 0.000 title claims abstract description 67
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 66
- 238000005530 etching Methods 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 238000011084 recovery Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 238000003860 storage Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 238000004064 recycling Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 25
- 229910052742 iron Inorganic materials 0.000 abstract description 21
- 239000002253 acid Substances 0.000 abstract description 12
- 239000000460 chlorine Substances 0.000 abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000006073 displacement reaction Methods 0.000 description 11
- 238000011010 flushing procedure Methods 0.000 description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 9
- 238000007792 addition Methods 0.000 description 9
- 229910001431 copper ion Inorganic materials 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 6
- 230000003113 alkalizing effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 5
- 235000019799 monosodium phosphate Nutrition 0.000 description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- -1 hydrogen ions Chemical class 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The utility model provides a recovery device for copper-containing etching waste liquid, and belongs to the technical field of acid etching waste liquid recovery. The method solves the problems of low copper product yield and purity, difficult polymerization in the process of producing polyiron, chlorine leakage, exceeding of total nitrogen in wastewater and the like in the existing recovery of acidic etching waste liquid. The device comprises a first-stage replacement reaction kettle with a first feeding hole, a first-stage centrifugal separation structure connected with the first-stage replacement reaction kettle, a second-stage replacement reaction kettle with a second feeding hole, a second-stage centrifugal separation structure connected with the second-stage replacement reaction kettle, and an oxidation polymerization reaction kettle with a dosing hole. The method is characterized in that iron and aluminum are adopted to realize primary replacement in a primary replacement reaction kettle, aluminum is adopted to realize secondary replacement in a secondary replacement reaction kettle to recycle copper, waste liquid after replacement is subjected to oxidation, hydrolysis and polymerization in an oxidation polymerization reaction kettle to prepare liquid polyaluminium ferric chloride, so that the acid etching waste liquid is completely recycled, and no waste water, waste gas and solid waste are discharged.
Description
Technical Field
The utility model belongs to the technical field of acid etching waste liquid recovery, and relates to a recovery device for copper-containing etching waste liquid.
Background
Etching copper is one of the most important procedures in the PCB production process, and copper-containing etching liquid is widely applied to the PCB etching process due to the advantages of high etching rate, stability, easiness in control and the like, but as etching is carried out, the content of copper ions is increased, the etching capability of the copper ions is weakened after the copper ions reach a certain concentration, the etching speed is greatly reduced, the solution stability is poor, crystallization and precipitation are easy, and further, the copper-containing etching liquid cannot meet the requirements of industrial production etching procedures and is discharged as waste liquid, so that a large amount of etching waste liquid is generated. The acid etching waste liquid is a dangerous waste with higher copper content and higher acidity generated in the copper foil etching process, and 60% of the etching waste liquid generated in the PCB industry in China is acid copper chloride etching waste liquid. The main components of the catalyst are copper chloride, hydrogen chloride and the like, wherein the mass concentration of the copper is 90-120 g/L, the concentration of the hydrogen chloride is 2-4 mol/L, has extremely high recycling value, and if discharged into the environment, not only causes resource waste, but also causes serious harm to the ecological environment.
The metal replacement method is used for recycling the acid etching waste liquid in the chemical method, so that copper can be recycled in a simple substance form, and the method can be widely applied. Based on the difference of metal activity, iron powder or aluminum powder is added into acid etching waste liquid, copper chloride complex ions are dissociated and reduced into sponge copper, and hydrochloric acid in the waste liquid can also react with iron or aluminum to be converted into polymeric ferric chloride or polymeric aluminum chloride water treatment flocculant.
For example, the Chinese patent of patent number 201210444645.5 discloses a method for recycling the waste etching liquid of acid copper by iron replacement treatment, which adopts reduced iron powder to replace copper ions in the etching liquid and separates to obtain sponge copper and a solution containing a large amount of ferrous ions. And oxidizing ferrous ions into ferric ions through chlorine oxidation to obtain the ferric chloride water treatment agent. The treatment method enables copper ions and hydrochloric acid to be recycled, but the use of chlorine has the operation safety risk of leakage, and the problem that the economic value of ferric trichloride is low or even difficult to sell in actual sales.
For example, the Chinese patent with the patent number of CN1920071A discloses a method for extracting copper from the PCB acid etching waste liquid and co-producing modified polyiron, and the technology realizes the replacement copper extraction and the preparation of the modified polyiron, but has the advantages that the replacement reaction time is long, the total iron concentration of a final product is required to be regulated by adding chemical raw materials such as ferric salt and the like, and the process operation is complex; the use of the catalyst aluminum nitrate may cause problems such as exceeding of total nitrogen in wastewater.
Disclosure of Invention
The utility model aims to solve the problems in the prior art and provides a recovery device for copper-containing etching waste liquid, which can realize the complete recovery and utilization of the acidic etching waste liquid.
The aim of the utility model can be achieved by the following technical scheme:
the recovery device of the copper-containing etching waste liquid comprises a first-stage replacement reaction kettle with a first feeding hole, a first-stage centrifugal separation structure connected with the first-stage replacement reaction kettle, a second-stage replacement reaction kettle with a second feeding hole, a second-stage centrifugal separation structure connected with the second-stage replacement reaction kettle, and an oxidation polymerization reaction kettle with a dosing hole, wherein liquid separated by the first-stage centrifugal separation structure is conveyed to the second-stage replacement reaction kettle through a first conveying structure, and liquid separated by the second-stage centrifugal separation structure is conveyed to the oxidation polymerization reaction kettle through a second conveying structure.
The method is characterized in that iron and aluminum are adopted to realize primary replacement in a primary replacement reaction kettle, aluminum is adopted to realize secondary replacement in a secondary replacement reaction kettle to recycle copper, waste liquid after replacement is subjected to oxidation, hydrolysis and polymerization in an oxidation polymerization reaction kettle to prepare liquid polyaluminium ferric chloride, so that the acid etching waste liquid is completely recycled, and no waste water, waste gas and solid waste are discharged.
In the recovery device of copper-containing etching waste liquid, the first-stage centrifugal separation structure comprises a first-stage centrifugal machine and a first-stage buffer tank, the first-stage centrifugal machine is connected with a discharge port of the first-stage replacement reaction kettle through a first pipeline, the first-stage buffer tank is connected with a liquid outlet of the first-stage centrifugal machine through a second pipeline, and a first discharge valve is arranged on the first pipeline.
After the liquid in the primary replacement reaction kettle is replaced, a first discharge valve is opened, the liquid in the primary replacement reaction kettle enters a primary centrifugal machine, the liquid is separated by the primary centrifugal machine, and the liquid enters a primary buffer tank through a second pipeline.
In the recovery device of copper-containing etching waste liquid, the secondary centrifugal separation structure comprises a secondary centrifugal machine and a secondary buffer tank, the secondary centrifugal machine is connected with a discharge port of the secondary replacement reaction kettle through a third pipeline, the secondary buffer tank is connected with a liquid outlet of the secondary centrifugal machine through a fourth pipeline, and a second discharge valve is arranged on the third pipeline.
After the liquid in the secondary replacement reaction kettle is replaced, a second discharge valve is opened, the liquid in the secondary replacement reaction kettle enters a secondary centrifuge, the liquid is separated by the secondary centrifuge, and the liquid enters a secondary buffer tank through a fourth pipeline.
The primary and secondary centrifuges may be replaced with filter presses.
In the recovery device of copper-containing etching waste liquid, the recovery device further comprises a water storage tank, wherein the water storage tank is connected with the primary centrifugal machine through a first water washing pipe and connected with the secondary centrifugal machine through a second water washing pipe, and valves are respectively arranged on the first water washing pipe and the second water washing pipe.
In the recovery device for copper-containing etching waste liquid, one end, away from the primary centrifugal machine, of the first washing pipe and one end, away from the secondary centrifugal machine, of the second washing pipe are converged into a main pipe and then connected with the water storage tank, and a water suction pump is arranged on the main pipe.
In the recovery device of copper-containing etching waste liquid, the first conveying structure comprises a first conveying pipe with one end connected with the first-stage buffer tank and a first lifting pump arranged on the first conveying pipe, and the other end of the first conveying pipe is connected with the second-stage replacement reaction kettle.
In the recovery device of copper-containing etching waste liquid, the second conveying structure comprises a second conveying pipe with one end connected with the second-stage buffer tank and a second lifting pump arranged on the second conveying pipe, and the other end of the second conveying pipe is connected with the oxidative polymerization reaction kettle.
The first-stage replacement reaction kettle is connected with the liquid storage tank through the feed pipe, the liquid suction pump is arranged on the feed pipe, the liquid storage tank is used for storing copper-containing etching waste liquid, and the copper-containing etching waste liquid in the liquid storage tank can be pumped into the first-stage replacement reaction kettle during operation of the liquid suction pump.
The outlet of the oxidation polymerization reaction kettle is provided with a third discharge valve.
The recovery method of the recovery device of the copper-containing etching waste liquid comprises the following steps:
step one, delivering the copper-containing etching waste liquid into a first-stage replacement reaction kettle, adding a proper amount of iron material and aluminum material from a first feed port, and stirring for replacement reaction for a period of time.
And step two, opening a first discharge valve to enable materials in the primary replacement reaction kettle to flow into a primary centrifugal machine for centrifugal separation, and enabling primary centrifugal liquid generated by the centrifugal separation to flow into a primary buffer tank.
And thirdly, when no liquid flows into the inlet of the primary buffer tank, starting the water suction pump to send tap water in the water storage tank into the primary centrifugal machine, leaching solids in the primary centrifugal machine, and enabling flushing water to flow into the primary buffer tank automatically.
And fourthly, feeding the materials in the first-stage buffer tank into a second-stage replacement reaction kettle through a first feeding pipe under the action of a first lifting pump, and adding a proper amount of aluminum material from a second feeding hole for secondary replacement reaction for a period of time.
And fifthly, opening a second discharge valve to enable materials in the secondary replacement reaction kettle to flow into a secondary centrifugal machine for centrifugal separation, and enabling secondary centrifugal liquid generated by the centrifugal separation to flow into a secondary buffer tank.
And step six, when no liquid flows into the inlet of the secondary buffer tank, starting the water suction pump to send tap water in the water storage tank into the secondary centrifuge, leaching solids in the secondary centrifuge, and enabling flushing water to flow into the secondary buffer tank.
And seventhly, feeding the materials in the second-stage buffer tank into an oxidation polymerization reaction kettle through a second feeding pipe under the action of a second lifting pump, and adding a proper amount of hydrochloric acid and a proper amount of sodium chlorate from a dosing port for oxidation reaction for a period of time.
Step eight, after sampling and detecting that the content of ferrous ions in the solution in the oxidation polymerization reaction kettle is lower than 0.2%, adding an alkalizing agent from a medicine adding port to adjust the pH value of the solution to a specified range, and performing hydrolysis polymerization reaction; the alkalizing agent is one of sodium hydroxide, calcium aluminate, calcium oxide and calcium hydroxide, preferably 30% sodium hydroxide solution, and the pH value of the solution is adjusted to 1.0-2.0, and if the pH value of the solution is in the range after the oxidation is completed, the alkalizing agent can not be added.
And step nine, after the hydrolysis combination reaction is finished and the pH value of the solution is stable, adding a proper amount of sodium dihydrogen phosphate solution from a dosing port, standing and aging for a period of time.
And step ten, opening a third discharge valve, and storing or selling the prepared liquid polyaluminum ferric chloride product from the inflow ton bucket.
And step eleven, manually transferring the solid sponge copper products obtained by the centrifugation of the primary centrifugal machine and the secondary centrifugal machine into a dryer for drying, and then placing the solid sponge copper products into a ton bag for packing and selling.
The drier makes the water content of the solid sponge copper less than 1%.
In the method for recovering the copper-containing etching waste liquid, A is set as the molar quantity of copper ions in the copper-containing etching waste liquid, and B is set as the molar quantity of hydrogen ions in the copper-containing etching waste liquid;
in the first step, the addition amount (molar amount) of the iron material is = (0.06-0.25) x a+ (0.03-0.13) x B, and the addition amount (molar amount) of the aluminum material is = (0.45-0.56) x a+ (0.23-0.28) x B; and firstly, adding a proper amount of iron material and aluminum material, and stirring and carrying out displacement reaction for 2-3 hours.
In the fourth step, the addition amount (molar amount) of the aluminum material is = (0.05-0.06) x A+ (0.02-0.03) x B; step four, adding a proper amount of aluminum material, and stirring and carrying out displacement reaction for 2-3 hours; or adding aluminum material to react until the copper ion detection content in the replacement liquid (liquid in the secondary replacement reaction kettle) is less than 5mg/L and the pH=2-3.
In the method for recovering copper-containing etching waste liquid, the addition amount (molar amount) of the iron material in the first step is C, the addition amount (molar amount calculated as hydrogen ions) of hydrochloric acid in the seventh step is = (0.5-1.5) ×C, and the addition amount (molar amount) of sodium chlorate is = (0.16-0.18) ×C, and the oxidation reaction is carried out for 2-3 hours.
In the method for recovering copper-containing etching waste liquid, in the step nine, the addition amount (molar amount) of the sodium dihydrogen phosphate solution is = (0.02-0.05) x C, and the solution is aged for 8-12 hours.
The whole replacement process controls the adding proportion (molar ratio) of the iron material and the aluminum material to be 1:2-10. Namely, the ratio of the molar quantity of the iron material added in the first step to the total molar quantity of the aluminum material added in the first step and the fourth step is 1:2-10.
Compared with the prior art, the utility model has the following advantages:
the copper grade and the copper recovery rate can be obviously improved, the purity of the sponge copper reaches 93% -98%, and the recovery rate is higher than 98%; the defects of long reaction time, severe reaction, high replacement cost, severe operation environment and the like in the single iron and aluminum replacement process are overcome by the common replacement of iron and aluminum; the direct oxidation of sodium chlorate is adopted, so that the problems of safety risk and total nitrogen exceeding caused by the use of chlorine and sodium nitrite are avoided; co-production liquid polyaluminum ferric chloride meets HG/T5359-2018 standard requirements, and the product integrates the advantages of aluminum salt and ferric salt, and makes up A l (OH) which is easy to cause residues in water in polyaluminum 3 The disadvantage that the polyiron is easy to cause color residue is better in water treatment effect, and better in sales and economic value; no waste gas, waste water and solid waste are generated, and no pollution is caused to the environment.
Drawings
Fig. 1 is a schematic structural view of a recycling apparatus according to the present utility model.
FIG. 2 is a process flow diagram of the recovery method provided by the utility model.
In the figure, 1, a first feeding port; 2. a first-stage replacement reaction kettle; 3. a second feed port; 4. a second-stage replacement reaction kettle; 5. a medicine adding port; 6. an oxidative polymerization reaction kettle; 7. a primary centrifuge; 8. a first-stage buffer tank; 9. a first pipeline; 10. a second pipeline; 11. a first discharge valve; 12. a secondary centrifuge; 13. a second-stage buffer tank; 14. a third pipeline; 15. a fourth pipeline; 16. a second discharge valve; 17. a water storage tank; 18. a first water washing pipe; 19. a second water washing pipe; 20. a header pipe; 21. a water pump; 22. a first feed tube; 23. a first lift pump; 24. a second feed tube; 25. a second lift pump; 26. a third discharge valve; 27. a liquid storage tank; 28. and (5) a liquid pump.
Detailed Description
The following are specific embodiments of the present utility model and the technical solutions of the present utility model will be further described with reference to the accompanying drawings, but the present utility model is not limited to these embodiments.
The recovery device of copper-containing etching waste liquid as shown in fig. 1 comprises a primary replacement reaction kettle 2 with a first feeding hole 1 at the top, a primary centrifugal separation structure arranged below the primary replacement reaction kettle 2 and connected with the primary replacement reaction kettle 2, a secondary replacement reaction kettle 4 with a second feeding hole 3 at the top, a secondary centrifugal separation structure arranged below the secondary replacement reaction kettle 4 and connected with the secondary replacement reaction kettle 4, and an oxidative polymerization reaction kettle 6 with a chemical feeding hole 5 at the top, wherein a third discharge valve 26 is arranged at the outlet of the oxidative polymerization reaction kettle 6.
The liquid separated by the primary centrifugal separation structure is lifted to the secondary replacement reaction kettle 4 through the first conveying structure, and the liquid separated by the secondary centrifugal separation structure is lifted to the oxidation polymerization reaction kettle 6 through the second conveying structure.
As shown in FIG. 1, the device also comprises a liquid storage tank 27, wherein the liquid storage tank 27 is used for storing copper-containing etching waste liquid, an outlet of the liquid storage tank 27 is connected to the side upper part of the primary replacement reaction kettle 2 through a feed pipe, a liquid pump 28 is arranged on the feed pipe, and the liquid pump 28 can pump the copper-containing etching waste liquid in the liquid storage tank 27 into the primary replacement reaction kettle 2 when in operation.
As shown in fig. 1, the primary centrifugal separation structure comprises a primary centrifugal machine 7 arranged below the primary displacement reaction kettle 2 and a primary buffer tank 8 arranged below the primary centrifugal machine 7, wherein the primary centrifugal machine 7 is connected with a discharge port of the primary displacement reaction kettle 2 through a first pipeline 9, the primary buffer tank 8 is connected with a liquid outlet of the primary centrifugal machine 7 through a second pipeline 10, and a first discharge valve 11 is arranged on the first pipeline 9. After the liquid in the primary displacement reaction kettle 2 is displaced, a first discharge valve 11 is opened, the liquid in the primary displacement reaction kettle 2 enters a primary centrifugal machine 7, the liquid is separated by the primary centrifugal machine 7, the liquid enters a primary buffer tank 8 through a second pipeline 10, and then the solid sponge copper in the primary centrifugal machine 7 is dried and collected.
In some other embodiments, the primary centrifuge 7 is replaced by a filter press.
As shown in fig. 1, the secondary centrifugal separation structure comprises a secondary centrifugal machine 12 arranged below the secondary replacement reaction kettle 4 and a secondary buffer groove 13 arranged below the secondary centrifugal machine 12, wherein the secondary centrifugal machine 12 is connected with a discharge hole of the secondary replacement reaction kettle 4 through a third pipeline 14, the secondary buffer groove 13 is connected with a liquid outlet of the secondary centrifugal machine 12 through a fourth pipeline 15, and a second discharge valve 16 is arranged on the third pipeline 14. After the liquid in the secondary replacement reaction kettle 4 is replaced, a second discharge valve 16 is opened, the liquid in the secondary replacement reaction kettle 4 enters a secondary centrifuge 12, the liquid is separated by the secondary centrifuge 12, the liquid enters a secondary buffer tank 13 through a fourth pipeline 15, and then the solid sponge copper in the secondary centrifuge 12 is dried and collected.
In some other embodiments, the secondary centrifuge 12 is replaced by a filter press.
In order to facilitate leaching of the solid sponge copper, as shown in fig. 1, the solid sponge copper leaching device further comprises a water storage tank 17, wherein the water storage tank 17 is connected with the primary centrifugal machine 7 through a first water washing pipe 18 and is connected with the secondary centrifugal machine 12 through a second water washing pipe 19, and valves are respectively arranged on the first water washing pipe 18 and the second water washing pipe 19. One end of the first water washing pipe 18, which is far away from the primary centrifugal machine 7, and one end of the second water washing pipe 19, which is far away from the secondary centrifugal machine 12, are converged into a main pipe 20, and then are connected with the water outlet of the water storage tank 17, and a water pump 21 is arranged on the main pipe 20.
When spraying is needed, the water suction pump 21 works to enable water in the water storage tank 17 to enter the main pipe 20, solid sponge copper is leached through a flushing spray pipe and a nozzle arranged in the primary centrifugal machine 7 according to the opening condition of a valve, flushing water flows into the primary buffer tank 8, or solid sponge copper is leached through a flushing spray pipe and a nozzle arranged in the secondary centrifugal machine 12, and flushing water flows into the secondary buffer tank 13.
As shown in fig. 1, the first conveying structure comprises a first conveying pipe 22 with one end connected with the primary buffer tank 8 and a first lift pump 23 arranged on the first conveying pipe 22, and the other end of the first conveying pipe 22 is communicated with the side upper part of the secondary replacement reaction kettle 4.
As shown in fig. 1, the second conveying structure includes a second feed pipe 24 having one end connected to the secondary buffer tank 13 and a second lift pump 25 provided on the second feed pipe 24, and the other end of the second feed pipe 24 communicates with the side upper portion of the oxidative polymerization reaction vessel 6.
As shown in fig. 2, the method for recovering copper-containing etching waste liquid comprises the following steps:
the copper-containing etching waste liquid in the liquid storage tank 27 is sent into the primary displacement reaction kettle 2 through a lateral feeding hole at the upper part of the primary displacement reaction kettle 2 by a liquid pump 28, and iron and aluminum are manually fed from a first feeding hole 1 at the top, wherein the feeding amount (molar amount) of iron is = (0.06-0.25) x A+ (0.03-0.13) x B, and the feeding amount (molar amount) of aluminum is = (0.45-0.56) x A+ (0.23-0.28) x B; a is the molar quantity of copper ions in the copper-containing etching waste liquid, and B is the molar quantity of hydrogen ions in the copper-containing etching waste liquid.
After stirring and displacement reaction for 2-3 hours, a first discharge valve 11 is opened to enable materials in the primary displacement reaction kettle 2 to flow into a primary centrifuge 7 positioned below the primary displacement reaction kettle 2 for centrifugal separation, primary centrifugal liquid generated by centrifugation flows into a primary buffer tank 8 from a second pipeline 10 at the bottom of the primary centrifuge 7, when no liquid flows into an inlet of the primary buffer tank 8 is observed, a valve on a first water washing pipe 18 is opened, a water suction pump 21 is started to send tap water in a water storage tank 17 into the primary centrifuge 7 through a main pipe 20 and the first water washing pipe 18, solid sponge copper is leached through a flushing spray pipe and a spray nozzle arranged in the primary centrifuge 7, and flushing water flows into the primary buffer tank 8 from the same.
Materials in the first-stage buffer tank 8 enter the second-stage replacement reaction kettle 4 through a first lifting pump 23 and a lateral feed inlet at the upper part of the second-stage replacement reaction kettle 4, aluminum materials are manually added from a second feed inlet 3 at the top to carry out a second replacement reaction, the addition amount (molar amount) of aluminum is = (0.05-0.06) x A+ (0.02-0.03) x B, and the replacement reaction is stirred for 2-3 hours; or adding waste aluminum to react until the copper ion detection content in the replacement liquid is less than 5mg/L and the pH value is=2-3.
And when no liquid flows into the inlet of the secondary buffer tank 13, a valve on the second water washing pipe 19 is opened, a water pump 21 is started to send tap water in the water storage tank 17 into the secondary centrifuge 12 through a main pipe 20 and the second water washing pipe 19, solid sponge copper is leached through a flushing spray pipe and a spray nozzle arranged in the secondary centrifuge 12, and flushing water also flows into the secondary buffer tank 13.
The materials in the secondary buffer tank 13 are pumped by a second lifting pump 25, enter the oxidation polymerization reaction kettle 6 through a lateral feed inlet at the upper part of the oxidation polymerization reaction kettle 6, hydrochloric acid is added into the oxidation polymerization reaction kettle 6 through a top drug adding port 5 of the acid adding unit, sodium chlorate is added from the top drug adding port 5 of the oxidation polymerization reaction kettle 6 through a manual or oxidant adding unit, the hydrochloric acid adding amount (calculated by hydrogen ions) is calculated by mol number of = (0.5-1.5) x C, sodium chlorate adding amount (calculated by mol number of = (0.16-0.18) x C, C is iron powder adding amount (calculated by mol number of) and is oxidized for 2-3 hours, after the content of ferrous ions in a sampling detection solution is lower than 0.2%, sodium hydroxide solution is added from the top drug adding port 5 of the reaction kettle through an alkalizing agent adding unit to adjust the pH value of 30% sodium hydroxide solution to be 1.0-2.0 for hydrolysis polymerization reaction, after the hydrolysis polymerization reaction is completed, sodium dihydrogen phosphate is added from the top drug adding port 5 of the reaction kettle to the top of the reaction kettle to be added with sodium dihydrogen phosphate by mol number of = (0.16-0.8) x C, and the sodium dihydrogen phosphate is added by a stabilizer drug adding unit to the liquid is discharged by mol number of = (0.26.05) x 6.02-6, and the reaction kettle is kept standing for aging after the reaction is cooled, the reaction kettle is cooled, the reaction liquid is cooled, and the reaction liquid is cooled. In this process, when ph=1.0 to 2.0 of the solution after completion of oxidation, an alkalizing agent may not be added.
And (3) manually transferring the solid sponge copper product obtained by the centrifugation of the primary centrifugal machine 7 and the secondary centrifugal machine 12 into a dryer for drying until the water content is less than 1%, and then placing the solid sponge copper product into a ton bag for packaging and selling.
The whole replacement process controls the adding proportion (molar ratio) of the iron material and the aluminum material to be 1:2-10. Namely, the ratio of the molar quantity of the iron material added into the primary replacement reaction kettle to the total molar quantity of the aluminum material added into the secondary replacement reaction kettle and the primary replacement reaction kettle is 1:2-10.
The iron material in the method is preferably iron powder, and can be replaced by waste iron, scrap iron and the like. The aluminum material is preferably waste aluminum, and can be replaced by finished aluminum and aluminum scraps. Besides sodium hydroxide solution as alkalizing agent, calcium aluminate, calcium oxide and calcium hydroxide can be used instead. Sulfuric acid can be used instead of hydrochloric acid, and hydrogen peroxide can be used instead of sodium chlorate.
The method adopts iron and aluminum to realize primary replacement in the primary replacement reaction kettle 2, adopts aluminum to realize secondary replacement in the secondary replacement reaction kettle 4 to recycle copper, and prepares liquid polyaluminium ferric chloride by oxidation, hydrolysis and polymerization of waste liquid after replacement in the oxidation polymerization reaction kettle 6, so that the acid etching waste liquid is completely recycled, and no waste water, waste gas and solid waste are discharged.
In this example, the chemical formula of the substitution reaction is:
Fe+CuCl 2 →FeCl 2 +Cu↓；
2Al+3CuCl 2 →2AlCl 3 +3Cu↓；
Fe+2HCl→FeCl 2 +H 2 ↑；
2Al+6HCl→2AlCl 3 +3H 2 ↑。
the chemical formula of the oxidation reaction is:
6FeCl 2 +NaClO 3 +6HCl→6FeCl 3 +NaCl+3H 2 O。
the chemical formula of the hydrolysis reaction is as follows:
2FeCl 3 +nH 2 O→Fe 2 (OH) n Cl 6-n +nHCl；
2AlCl 3 +nH 2 O→Al 2 (OH) n Cl 6-n +nHCl。
the chemical formula of the polymerization reaction is:
mFe 2 (OH) n Cl 6-n +mAl 2 (OH) n Cl 6-n →
[Al 2 (OH) n Cl 6-n ] m [Fe 2 (OH) n Cl 6-n ] m (1≤n≤5≤m≤10)。
the specific embodiments described herein are offered by way of example only to illustrate the spirit of the utility model. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the utility model or exceeding the scope of the utility model as defined in the accompanying claims.
Claims (7)
1. The utility model provides a recovery unit of copper-containing etching waste liquid, a serial communication port, including first level replacement reation kettle (2) that have first feed inlet (1), the one-level centrifugal separation structure of being connected with first level replacement reation kettle (2), second level replacement reation kettle (4) that have second feed inlet (3), the second level centrifugal separation structure of being connected with second level replacement reation kettle (4), and oxidation polymerization reation kettle (6) that have charge mouth (5), the liquid that is separated by first level centrifugal separation structure is carried to second level replacement reation kettle (4) through first conveying structure, the liquid that is separated by second level centrifugal separation structure is carried to oxidation polymerization reation kettle (6) through second conveying structure.
2. The copper-containing etching waste liquid recycling device according to claim 1, wherein the primary centrifugal separation structure comprises a primary centrifugal machine (7) and a primary buffer tank (8), the primary centrifugal machine (7) is connected with a discharge port of the primary replacement reaction kettle (2) through a first pipeline (9), the primary buffer tank (8) is connected with a liquid outlet of the primary centrifugal machine (7) through a second pipeline (10), and a first discharge valve (11) is arranged on the first pipeline (9).
3. The copper-containing etching waste liquid recycling device according to claim 2, wherein the secondary centrifugal separation structure comprises a secondary centrifugal machine (12) and a secondary buffer tank (13), the secondary centrifugal machine (12) is connected with a discharge port of the secondary replacement reaction kettle (4) through a third pipeline (14), the secondary buffer tank (13) is connected with a liquid outlet of the secondary centrifugal machine (12) through a fourth pipeline (15), and a second discharge valve (16) is arranged on the third pipeline (14).
4. The copper-containing etching waste liquid recovery device according to claim 3, further comprising a water storage tank (17), wherein the water storage tank (17) is connected with the primary centrifuge (7) through a first water washing pipe (18) and is connected with the secondary centrifuge (12) through a second water washing pipe (19), and valves are respectively arranged on the first water washing pipe (18) and the second water washing pipe (19).
5. The copper-containing etching waste liquid recovery device according to claim 4, wherein one end of the first water washing pipe (18) far away from the primary centrifugal machine (7) and one end of the second water washing pipe (19) far away from the secondary centrifugal machine (12) are converged into a main pipe (20) and then connected with the water storage tank (17), and a water suction pump (21) is arranged on the main pipe (20).
6. The copper-containing etching waste liquid recovery device according to claim 2, wherein the first conveying structure comprises a first conveying pipe (22) with one end connected with the primary buffer tank (8) and a first lifting pump (23) arranged on the first conveying pipe (22), and the other end of the first conveying pipe (22) is connected with the secondary replacement reaction kettle (4).
7. A copper-containing etching waste liquid recycling apparatus according to claim 3, wherein the second conveying structure comprises a second conveying pipe (24) with one end connected with the second-stage buffer tank (13) and a second lifting pump (25) arranged on the second conveying pipe (24), and the other end of the second conveying pipe (24) is connected with the oxidation polymerization reaction kettle (6).
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